CN106939014A - A kind of quaternary phosphonium salt ionic liquid and its production and use - Google Patents
A kind of quaternary phosphonium salt ionic liquid and its production and use Download PDFInfo
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- CN106939014A CN106939014A CN201610004714.9A CN201610004714A CN106939014A CN 106939014 A CN106939014 A CN 106939014A CN 201610004714 A CN201610004714 A CN 201610004714A CN 106939014 A CN106939014 A CN 106939014A
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- ionic liquid
- phosphonium salt
- quaternary phosphonium
- salt ionic
- quaternary
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 74
- 150000004714 phosphonium salts Chemical group 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000005886 esterification reaction Methods 0.000 claims abstract description 34
- 230000032050 esterification Effects 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 239000005416 organic matter Substances 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- -1 phosphine salt ion Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 19
- 229910019142 PO4 Inorganic materials 0.000 description 16
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 8
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- MJRPMUINYAOXRW-UHFFFAOYSA-N tributylphosphane;hydrochloride Chemical compound [Cl-].CCCC[PH+](CCCC)CCCC MJRPMUINYAOXRW-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UJHVZVXYELCZLX-UHFFFAOYSA-M tributyl(dodecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC UJHVZVXYELCZLX-UHFFFAOYSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GRFKUEDWLAGOJX-UHFFFAOYSA-N acetic acid;butyl acetate Chemical compound CC(O)=O.CCCCOC(C)=O GRFKUEDWLAGOJX-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HGJLYMGBCAKBLK-UHFFFAOYSA-N sodium;trifluoromethanesulfonic acid Chemical compound [Na].OS(=O)(=O)C(F)(F)F HGJLYMGBCAKBLK-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- KUNICNFETYAKKO-UHFFFAOYSA-N sulfuric acid;pentahydrate Chemical compound O.O.O.O.O.OS(O)(=O)=O KUNICNFETYAKKO-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/50—Non-coordinating groups comprising phosphorus
- B01J2540/54—Quaternary phosphonium groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of quaternary phosphonium salt ionic liquid, its formula is [Bu3PR]+X-, R is C6-C16Straight or branched alkyl, X-For p-C7H7SO3 -、CF3SO3 -、HSO4 -Or H2PO4 -.Present invention also offers a kind of preparation method of quaternary phosphonium salt ionic liquid, this method includes：Under the conditions of ion-exchange reactions, ion-exchange reactions is occurred into for mono- quaternary alkylphosphonium salts and Bronsted acid, product of contact is obtained；Wherein, the formula of the mono- quaternary alkylphosphonium salts is [Bu3PR]+Z-, R is C6-C16Straight or branched alkyl, Z is halogen；The Bronsted acid is p-C7H7SO3H、CF3SO3H、H2SO4Or H3PO4.Present invention also offers purposes of the quaternary phosphonium salt ionic liquid in catalytic esterification.By above-mentioned technical proposal, the quaternary phosphonium salt ionic liquid that the present invention is provided is in the esterification being catalyzed between carboxylic acid and organic matter containing hydroxyl, and catalytic activity is high, and reaction selectivity is high, and accessory substance is few, and it is high to recycle performance.
Description
Technical field
The present invention relates to organic chemistry filed, in particular it relates to a kind of quaternary phosphonium salt ionic liquid and its preparation
Method and purposes.
Background technology
Ionic liquid is also known as low-temperature molten salt, and ionic liquid has physical and chemical stability good, liquid temperature model
Enclose wide, steam force down and also it is not volatile, all have good dissolubility energy and pole to organic and inorganic matter
Property unique physical property such as controllable, it is generally considered with wide application prospect, can replace biography
The environmentally friendly solvent of system organic solvent, but also catalyst can be also served as, in such as organic synthesis, resist
The technical field of bacterium material, hybrid inorganic-organic materials, electromagnetic material etc. has application.
Esterification is the important chemical reaction of a class, is that carboxylic acid or oxygen-containing inorganic acid generate ester and water with alcohol
Reaction.The esterification of carboxylic acid and alcohol is reversible, and General reactions are extremely slow, it is necessary to use
Catalyst improves reaction rate, is traditionally used as catalyst using the concentrated sulfuric acid, although make using the concentrated sulfuric acid
Cheap for catalyst, product quality is more stable, but also has following limitation：When the dense sulphur of use
When acid is as catalyst, concentrated sulfuric acid consumption is big and can not recycle, so as to produce substantial amounts of spent acid, separately
Outside, the concentrated sulfuric acid there are problems that corrosivity is strong, post processing is difficult and can not, and the concentrated sulfuric acid
During as catalyst esterification, the production cycle is long, and reaction selectivity is poor.
Therefore, high in the urgent need to developing a kind of catalytic activity, reaction selectivity is high, while can circulate makes again
Catalyst for esterification reaction.
The content of the invention
In order to which the corrosivity for the traditional catalyst concentrated sulfuric acid for overcoming esterification is strong, reaction selectivity is poor and nothing
The defect that method is recycled, has catalytic activity height, reaction choosing to esterification the invention provides a kind of
Selecting property is high and can recycle quaternary phosphonium salt ionic liquids and its production and use.
It is an object of the invention to provide a kind of quaternary phosphonium salt ionic liquid, the formula of the quaternary phosphonium salt ionic liquid is
[Bu3PR]+X-, R is C6-C16Straight or branched alkyl, wherein, X-For p-C7H7SO3 -、CF3SO3 -、
HSO4 -Or H2PO4 -。
The invention provides a kind of preparation method of quaternary phosphonium salt ionic liquid catalyst, this method includes：
Under the conditions of ion-exchange reactions, mono- quaternary alkylphosphonium salts are contacted with Bronsted acid, product of contact is obtained；Wherein,
The formula of the mono- quaternary alkylphosphonium salts is [Bu3PR]+Z-, R is C6-C16Straight or branched alkyl, Z is
Halogen；The formula of the Bronsted acid is H+X-, X-Selected from p-C7H7SO3 -、CF3SO3 -、HSO4 -With
H2PO4 -In at least one.
The invention provides the preparation-obtained quaternary phosphonium salt ionic liquid of above-mentioned preparation method.
Present invention also offers purposes of the above-mentioned quaternary phosphonium salt ionic liquid in catalytic esterification.
By above-mentioned technical proposal, the present invention provides quaternary phosphonium salt ionic liquids in catalysis carboxylic acid and contains hydroxyl
During esterification between the organic matter of base, catalyst activity is high, and reaction selectivity is high, accessory substance
It is few, and it is high to recycle performance.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is [Bu3PC14H29]+Cl-TG and DSC curve figure；
Fig. 2 is [Bu3PC14H29]+[PTSA]-TG and DSC curve figure；
Fig. 3 is [Bu3PC14H29]+[CF3SO3]-TG and DSC curve figure；
Fig. 4 is [Bu3PC14H29]+[HSO4]-TG and DSC curve figure；
Fig. 5 is [Bu3PC14H29]+[H2PO4]-TG and DSC curve figure；
Fig. 6 is [Bu3PC14H29]+Cl-'sInfrared spectrogram (2958 cm-1、2928 cm-1And 2858 cm-1
Respectively methyl, methylene stretching vibration absworption peak, 1464 cm-1And 1415 cm-1Bent for methylene
Vibration absorption peak, 1378 cm-1For C-P stretching vibration absworption peaks)；
Fig. 7 is [Bu3PC14H29]+[PTSA]-Infrared spectrogram ([Bu3PC14H29]+[PTSA]-With
[Bu3PC14H29]+Cl-Cation is identical, and methyl, methylene absworption peak wave number are identical.1196 cm-1For
O=S=O antisymmetric stretching vibration absworption peaks, 1121 cm-1For S=O stretching vibration absworption peaks, 1017 cm-1
For O=S=O symmetrical stretching vibrations absworption peak)；
Fig. 8 is [Bu3PC14H29]+[CF3SO3]-Infrared spectrogram (1259 cm-1Oppose for O=S=O
Claim stretching vibration absworption peak, 1151 cm-1For S=O stretching vibration absworption peaks, 1032 cm-1For O=S=O
Symmetrical stretching vibration absworption peak)；
Fig. 9 is [Bu3PC14H29]+[HSO4]-Infrared spectrogram (1233 cm-1For O=S=O antisymmetry
Stretching vibration absworption peak, 1162 cm-1For S=O stretching vibration absworption peaks, 1058 cm-1For O=S=O pairs
Claim stretching vibration absworption peak)；
Figure 10 is [Bu3PC14H29]+[H2PO4]-Infrared spectrogram (969 cm-1Symmetrically stretched for phosphate radical
Contracting vibration, 1097 cm-1For the asymmetric stretching vibration of phosphate radical).
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Embodiment described herein is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of quaternary phosphonium salt ionic liquid, the formula of the quaternary phosphonium salt ionic liquid is
[Bu3PR]+X-, R is C6-C16Straight or branched alkyl, and X-For p-C7H7SO3 -、CF3SO3 -、
HSO4 -Or H2PO4 -。
Wherein, the C6-C16The instantiation of straight or branched alkyl can include but is not limited to：Just
Hexyl, n-octyl, positive decyl, dodecyl, n-tetradecane base or n-hexadecyl.
According to quaternary phosphonium salt ionic liquids of the present invention, it is preferable that R is C8-C14Straight or branched alkyl,
X-Can be p-C7H7SO3 -Or CF3SO3 -.Under the preferable case, Gai is used for quaternary phosphonium salt ionic liquid
During esterification between carboxylic acid and organic matter containing hydroxyl, there can be higher catalytic activity and urge
Change reaction selectivity.Wherein, the C8-C14Straight or branched alkyl can be for example n-octyl, just
Dodecyl or n-tetradecane base.
Present invention also offers a kind of preparation method of quaternary phosphonium salt ionic liquid, this method includes：In ion
Under the conditions of exchange reaction, mono- quaternary alkylphosphonium salts are contacted with Bronsted acid, product of contact is obtained；Wherein, it is described
The formula of mono- quaternary alkylphosphonium salts is [Bu3PR]+Z-, R is C6-C16Straight or branched alkyl, Z is halogen；
The formula of the Bronsted acid is H+X-, X-Selected from p-C7H7SO3 -、CF3SO3 -、HSO4 -And H2PO4 -
In at least one.
Wherein, the C6-C16The instantiation of straight or branched alkyl can include but is not limited to：Just
Hexyl, n-octyl, positive decyl, dodecyl, n-tetradecane base or n-hexadecyl.
According to the preparation method of quaternary phosphonium salt ionic liquid of the present invention, it is preferable that R is C8-C14Straight chain or
Branched alkyl；Z is chlorine；X-For p-C7H7SO3 -Or CF3SO3 -.Under the preferable case, the quaternary phosphine
When ionic liquid is used for the esterification between carboxylic acid and organic matter containing hydroxyl, can have higher
Catalytic activity and catalytic reaction selectivity.Wherein, the C8-C14Straight or branched alkyl for example may be used
Think n-octyl, dodecyl or n-tetradecane base.
Wherein, the mono- quaternary alkylphosphonium salts can be commercially available, it would however also be possible to employ those skilled in the art
Well known method is prepared, and the mono- quaternary alkylphosphonium salts can for example include but is not limited to [Bu3PC12H25]+
Cl-, [Bu3PC14H29]+Cl-, [Bu3PC10H21]+Cl-[Bu3PC8H17]+Cl-。
According to the preparation method of quaternary phosphonium salt ionic liquid of the present invention, the Bronsted acid is that liquid or solid-state are analyzed
Pure reagent.The consumption of the mono- quaternary alkylphosphonium salts and the consumption of the Bronsted acid do not have particular/special requirement, as long as energy
The consumption of generation ion-exchange reactions, preferably Bronsted acid is the mono- quaternary alkylphosphonium salts is reacted completely,
The amount of reaction Bronsted acid used is with anion Z contained in mono- quaternary alkylphosphonium salts completely-Amount calculate.
Wherein, in order that halide ion is exchanged by Bronsted acid as thoroughly as possible, target quaternary alkylphosphonium salt is improved
The purity of ionic liquid, and then improve under the catalytic activity of quaternary phosphonium salt ionic liquid, preferable case, relatively
In 1 mole of the mono- quaternary alkylphosphonium salts, the consumption of the Bronsted acid is 1-2 moles, the Bronsted acid
Consumption is with the X in the Bronsted acid-Amount calculate.It is highly preferred that the first season relative to 1 mole
Phosphonium salt, the consumption of the Bronsted acid can be 1.01-1.2 moles.
According to the preparation method of quaternary phosphonium salt ionic liquid of the present invention, it is preferable that the ion-exchange reactions bar
Part can include：Temperature is 85-100 DEG C, and the time is 12-20 hours.
According to the preparation method of quaternary phosphonium salt ionic liquid of the present invention, in order to further purify the quaternary alkylphosphonium salt from
Sub- liquid, improves the catalytic activity of quaternary phosphonium salt ionic liquid, the preparation side of quaternary phosphonium salt ionic liquid of the present invention
Method also includes：It is 2~4 that product obtained by mono- quaternary alkylphosphonium salts are contacted with Bronsted acid, which is washed to pH value,
Obtain washing product；Then the washing product is subjected to vacuum distillation and suction filtration, obtains product quaternary alkylphosphonium salt
Ionic liquid.The washing be it is well-known to those skilled in the art, for example can be with corresponding with Bronsted acid
Alkali metal salt M+X-Saturated aqueous solution is washed, and is given birth to removing excessive Bronsted acid and ion-exchange reactions
Into halogen acids, then by after the washing product carry out vacuum distillation remove residual moisture, cooling
Carry out suction filtration again afterwards and remove a small amount of salinity separated out, obtained filtrate is target quaternary phosphonium salt ionic liquid.
According to the preparation method of quaternary phosphonium salt ionic liquid of the present invention, in order to improve the production of reaction rate and product
Rate, it is preferable that the ion-exchange reactions condition can include：Temperature is 90-95 DEG C, and the time is 16-20
Hour.
The invention provides the preparation-obtained quaternary phosphonium salt ionic liquid of above-mentioned preparation method.
Present invention also offers purposes of the above-mentioned quaternary phosphonium salt ionic liquid in catalytic esterification.
Specifically, the esterifying reaction method is included under the conditions of esterification and in above-mentioned quaternary phosphine salt ion
In the presence of liquid, carboxylic acid is contacted with the organic matter containing hydroxyl, under preferable case, by carboxylic acid and contained
The organic matter of hydroxyl is contacted under agitation, so advantageously ensure that quaternary phosphonium salt ionic liquid and carboxylic acid and
Organic matter containing hydroxyl is sufficiently mixed, so as to play good catalytic action.The mode of the stirring can
The conventional selection of this area is thought, such as can use mechanical agitation, ultrasonic agitation.The stirring
Intensity can be well mixed as base with organic matter of the quaternary phosphonium salt ionic liquid with carboxylic acid and containing hydroxyl
This those skilled in the art can be known, repeated no more by standard.
It is anti-in order to improve according to purposes of the above-mentioned quaternary phosphonium salt ionic liquid of the invention in catalytic esterification
Answer the yield of speed and product, and reduction production cost, it is preferable that with carboxylic acid and contain the organic of hydroxyl
On the basis of the gross weight of thing, the consumption of the quaternary phosphonium salt ionic liquid is 3-20 weight %, it is highly preferred that
On the basis of the gross weight of organic matter by carboxylic acid and containing hydroxyl, the quaternary phosphonium salt ionic liquid catalyst
Consumption is 5-15 weight %.
The species and consumption of organic matter of the invention to the carboxylic acid and containing hydroxyl are not limited especially
It is fixed, for example, the carboxylic acid can be selected from the one or more in acetic acid, propionic acid, acrylic acid and benzoic acid；
The organic matter containing hydroxyl can be alcohol and/or phenol, be specifically as follows methanol, ethanol, n-butanol,
At least one in isopropanol and n-octyl alcohol.In addition, the consumption of the carboxylic acid and the organic matter containing hydroxyl
Reasonable selection can be carried out according to actual conditions, in order to improve the yield of reaction speed and product, it is preferable that
The mol ratio of the acid and organic matter containing hydroxyl is 1: 0.1-10, it is highly preferred that the acid and containing
The mol ratio for having the organic matter of hydroxyl can be 1: 0.2-5.
According to purposes of the above-mentioned quaternary phosphonium salt ionic liquid of the invention in catalytic esterification, the esterification is anti-
The conventional selection that condition can be this area is answered, as a rule, the esterification condition includes reaction temperature
Degree and reaction time.Wherein, the reaction temperature can be carried out within the scope of wider temperature, usual feelings
Under condition, in order to further be beneficial to the progress of reaction, the reaction temperature is usually the backflow temperature of reaction system
Degree.The extension in reaction time is conducive to the raising of the conversion ratio of reactant and the yield of reaction product, still
The increase rate of the yield of reaction time long conversion ratio and reaction product to reactant is not obvious.
According to purposes of the above-mentioned quaternary phosphonium salt ionic liquid of the invention in catalytic esterification, esterification knot
Shu Hou, by obtained ester and the carboxylic acid not reacted completely and/or can contain hydroxyl by way of distillation
Organic matter separated from the obtained product of contact；Distilling remaining bottom liquid can be as esterification
Catalyst recycle.
The present invention will be described in further detail by following examples below.It is used in the present invention
Instrument and reagent unless otherwise instructed, are instrument and reagent commonly used in the art.
Embodiment 1
At room temperature, n-tetradecane base tributyl phosphonium chloride (is purchased from Beijing Rui Shibang fine chemical technologies
Co., Ltd) add in the reaction bulb with stirring, thermometer and reflux condensation mode, stirring is opened, then
P-methyl benzenesulfonic acid (english abbreviation is added portionwise：PTSA, AR recovers essence purchased from Tianjin
Thin chemical institute), it is to slowly warm up to 100 DEG C, insulation reaction 18 hours；Wherein, rubbed relative to 1
Your n-tetradecane base tributyl phosphonium chloride, the consumption of p-methyl benzenesulfonic acid is 1.05 moles.
After reaction terminates, it is 2~3 that reaction product is washed into pH with p-methyl benzenesulfonic acid saturated aqueous solution of sodium,
Then the organic layer after washing is subjected to vacuum distillation water removal, carries out suction filtration after cooling again, remove what is separated out
A small amount of salinity, obtains filtrate.Align tributyltetradecylphchloridem chloridem and filtrate carries out TG and DSC
And infrared spectrum analysis, TG and DSC curve figure be shown in Fig. 1 and Fig. 2 respectively, and infrared spectrogram is shown in respectively
Fig. 6 and Fig. 7, wherein, [Bu3PC14H29]+[PTSA]-With [Bu3PC14H29]+Cl-Cation is identical,
Methyl, methylene absworption peak wave number are identical.1196cm-1For O=S=O antisymmetric stretching vibration absworption peaks,
1121cm-1For S=O stretching vibration absworption peaks, 1017cm-1For O=S=O symmetrical stretching vibration absworption peaks,
Prove that obtained filtrate is quaternary phosphonium salt ionic liquid [Bu3PC14H29]+[PTSA]-。
Embodiment 2
At room temperature, n-tetradecane base tributyl phosphonium chloride (is purchased from Beijing Rui Shibang fine chemical technologies
Co., Ltd) add in the reaction bulb with stirring, thermometer and reflux condensation mode, stirring is opened, then
Trifluoromethanesulfonic acid (AR recovers fine chemistry industry research institute purchased from Tianjin), drop is slowly added dropwise
1h is stirred at room temperature after adding, 95 DEG C, insulation reaction 18 hours are then to slowly warm up to；Wherein,
The n-tetradecane base tributyl phosphonium chloride relative to 1 mole, the consumption of trifluoromethanesulfonic acid is 1.05
Mole.
After reaction terminates, it is 2~3 that reaction product is washed into pH with trifluoromethanesulfonic acid saturated aqueous solution of sodium,
Then the organic layer after washing is subjected to vacuum distillation water removal, carries out suction filtration after cooling again, remove what is separated out
A small amount of salinity, obtains filtrate.TG and DSC and infrared spectrum analysis, TG and DSC are carried out to filtrate
Curve map is shown in Fig. 3, and infrared spectrogram is shown in Fig. 8.Wherein, 1259cm-1Shaken for O=S=O antisymmetry is flexible
Dynamic absworption peak, 1151cm-1For S=O stretching vibration absworption peaks, 1032cm-1Symmetrically stretched for O=S=O
Vibration absorption peak, it was demonstrated that obtained filtrate is quaternary phosphonium salt ionic liquid [Bu3PC14H29]+[CF3SO3]-。
Embodiment 3
Using preparation method same as Example 2, quaternary phosphonium salt ionic liquid is prepared
[Bu3PC14H29]+[HSO4]-, difference is, by trifluoromethanesulfonic acid replace with the concentrated sulfuric acid (AR,
Purchased from Beijing Chemical Plant), substitute trifluoromethanesulfonic acid sodium saturation water with niter cake saturated aqueous solution during washing
Solution.TG and DSC and infrared spectrum analysis are carried out to filtrate, TG is shown in Fig. 4 with DSC curve figure,
Infrared spectrogram is shown in Fig. 9, wherein, 1233cm-1For O=S=O antisymmetric stretching vibration absworption peaks, 1162
cm-1For S=O stretching vibration absworption peaks, 1058cm-1For O=S=O symmetrical stretching vibration absworption peaks, i.e.,
Prove that obtained filtrate is quaternary phosphonium salt ionic liquid [Bu3PC14H29]+[HSO4]-。
Embodiment 4
Using preparation method same as Example 1, quaternary phosphonium salt ionic liquid is prepared
[Bu3PC14H29]+[H2PO4]-, difference is, by p-methyl benzenesulfonic acid replace with phosphoric acid (AR,
Purchased from Beijing Chemical Plant), substitute paratoluenesulfonic acid sodium salt saturation with potassium dihydrogen phosphate saturated aqueous solution during washing
The aqueous solution.TG and DSC and infrared spectrum analysis are carried out to filtrate, TG is shown in Fig. 5 with DSC curve figure,
Infrared spectrogram is shown in Figure 10, wherein, 969cm-1For phosphate radical symmetrical stretching vibration absworption peak, 1097cm-1
For the asymmetric stretching vibration absworption peak of phosphate radical, that is, prove obtained filtrate as quaternary phosphonium salt ionic liquid
[Bu3PC14H29]+[H2PO4]-。
Embodiment 5
At room temperature, dodecyl tributyl phosphonium chloride (is purchased from Beijing Rui Shibang fine chemical technologies
Co., Ltd) add in the reaction bulb with stirring, thermometer and reflux condensation mode, stirring is opened, then
P-methyl benzenesulfonic acid (AR recovers fine chemistry industry research institute purchased from Tianjin) is added portionwise, delays
Slowly 85 DEG C, insulation reaction 20 hours are warming up to；Wherein, the dodecyl relative to 1 mole
Tributyl phosphonium chloride, the consumption of p-methyl benzenesulfonic acid is 1.05 moles.
After reaction terminates, it is 2~3 that reaction product is washed into pH with p-methyl benzenesulfonic acid saturated aqueous solution of sodium,
Then the organic layer after washing is subjected to vacuum distillation water removal, carries out suction filtration after cooling again, remove what is separated out
A small amount of salinity, obtained filtrate (the anion absorption peak of infrared spectrogram is similar to Fig. 7, not shown)
As quaternary phosphonium salt ionic liquid [Bu3PC12H25]+[PTSA]-。
Embodiment 6
At room temperature, dodecyl tributyl phosphonium chloride (is purchased from Beijing Rui Shibang fine chemical technologies
Co., Ltd) add in the reaction bulb with stirring, thermometer and reflux condensation mode, stirring is opened, then
Trifluoromethanesulfonic acid (AR recovers fine chemistry industry research institute purchased from Tianjin), drop is slowly added dropwise
1h is stirred at room temperature after adding, 100 DEG C, insulation reaction 12 hours are then to slowly warm up to；Wherein,
The dodecyl tributyl phosphonium chloride relative to 1 mole, the consumption of trifluoromethanesulfonic acid is 1.05
Mole.
After reaction terminates, it is 2~3 that reaction product is washed into pH with trifluoromethanesulfonic acid saturated aqueous solution of sodium,
Then the organic layer after washing is subjected to vacuum distillation water removal, carries out suction filtration after cooling again, remove what is separated out
A small amount of salinity, obtained filtrate (the anion absorption peak of infrared spectrogram is similar to Fig. 8, not shown)
As obtain quaternary phosphonium salt ionic liquid [Bu3PC12H25]+[CF3SO3]-。
Embodiment 7
Using preparation method same as Example 6, quaternary phosphonium salt ionic liquid is prepared
[Bu3PC12H25]+[HSO4]-(the anion absorption peak of infrared spectrogram is similar to Fig. 9, not shown),
Difference is that trifluoromethanesulfonic acid is replaced with into the concentrated sulfuric acid (AR, purchased from Beijing Chemical Plant),
During washing trifluoromethanesulfonic acid saturated aqueous solution of sodium is substituted with niter cake saturated aqueous solution.
Embodiment 8
Using preparation method same as Example 5, quaternary phosphonium salt ionic liquid is prepared
[Bu3PC12H25]+[H2PO4]-(the anion absorption peak of infrared spectrogram is similar to FIG. 10, not shown),
Difference is that p-methyl benzenesulfonic acid is replaced with into phosphoric acid (AR, purchased from Beijing Chemical Plant), water
When washing p-methyl benzenesulfonic acid saturated aqueous solution of sodium is substituted with potassium dihydrogen phosphate saturated aqueous solution.
Testing example 1
To mono- quaternary alkylphosphonium salts [Bu3PC14H29]+Cl-And the quaternary phosphine salt ion prepared in embodiment 1-4
Density, viscosity and the decomposition temperature of liquid are characterized, and the results are shown in Table 1-3.
The density of the quaternary phosphonium salt ionic liquid of table 1 at different temperatures, g/cm3
| Temperature, DEG C | 50 | 60 | 70 |
| [Bu3PC14H29]+Cl- | 0.88845 | 0.88252 | 0.87657 |
| [Bu3PC14H29]+[PTSA]- | 0.96901 | 0.96268 | 0.95635 |
| [Bu3PC14H29]+[CF3SO3]- | 0.99341 | 0.98676 | 0.98013 |
| [Bu3PC14H29]+[HSO4]- | 0.95702 | 0.95094 | 0.94491 |
| [Bu3PC14H29]+[H2PO4]- | 0.94678 | 0.94060 | 0.93439 |
The viscosity of the quaternary phosphonium salt ionic liquid of table 2 at different temperatures, cP
| Temperature, DEG C | 50 | 60 | 70 |
| [Bu3PC14H29]+Cl- | 286.32 | 168.13 | 101.75 |
| [Bu3PC14H29]+[PTSA]- | 197.16 | 117.08 | 73.75 |
| [Bu3PC14H29]+[CF3SO3]- | 149.20 | 92.87 | 60.88 |
| [Bu3PC14H29]+[HSO4]- | 620.60 | 361.36 | 226.50 |
| [Bu3PC14H29]+[H2PO4]- | 377.64 | 221.39 | 139.65 |
(Ti is temperature of initial decomposition to the decomposition temperature of the DTG of table 3 measure quaternary phosphonium salt ionic liquid, and Tf is most
Whole decomposition temperature)
| Ionic liquid | Ti, DEG C | Tf, DEG C |
| [Bu3PC14H29]+Cl- | 330 | 410 |
| [Bu3PC14H29]+[PTSA]- | 370 | 460 |
| [Bu3PC14H29]+[CF3SO3]- | 380 | 500 |
| [Bu3PC14H29]+[HSO4]- | 330 | 410 |
| [Bu3PC14H29]+[H2PO4]- | 360 | 510 |
Testing example 2
This testing example prepares quaternary phosphonium salt ionic liquids, the first season for testing example 1-8
Phosphonium salt ([Bu3PC14H29]+Cl-) and the traditional catalyst concentrated sulfuric acid be used for catalytic esterification catalytic activity
And selectivity.
Using acetic acid and n-butanol as raw material, the quaternary phosphine salt ion prepared respectively using embodiment 1-8
Liquid, mono- quaternary alkylphosphonium salts ([Bu3PC14H29]+Cl-) and the concentrated sulfuric acid (concentration is 98%, purchased from Beijing
Factory) as catalyst, the esterification of acetic acid and n-butanol is catalyzed, is comprised the following steps that：By acetic acid
With n-butanol mixing, above-mentioned catalyst is separately added into, the wherein gross weight of acetic acid and n-butanol is urged with described
The amount ratio of agent is 1：0.1, the mol ratio of acetic acid and n-butanol is 1：1.5, agitating heating works as body
System is when starting to distill out alcohol-water azeotrope, the start recording reaction time and and time-division water, control temperature keeps
Backflow, the liquid weight being collected into water knockout drum is not further added by, and stops reaction, recording reacting time
(being shown in Table 4).
By obtained above-mentioned reaction system, distilled, untill the weight of the cut steamed is not further added by,
The crude product cut and distillation residue of n-butyl acetate are finally given, wherein the distillation residue is season
Phosphonium salt ionic liquid.Using gas chromatography, obtained above-mentioned n-butyl acetate crude product cut is carried out
Detection and analysis, as a result as shown in table 4.
By above-mentioned distillation residue quaternary phosphonium salt ionic liquid carry out it is secondary reuse, specific steps with it is above-mentioned
Step is identical, and recording reacting time (is shown in Table 4).And distilled obtained reaction system, to no longer
Have untill cut steams, obtain the crude product cut and distillation residue quaternary alkylphosphonium salt ionic liquid of n-butyl acetate
Body.Using gas chromatography, obtained above-mentioned n-butyl acetate crude product cut is tested and analyzed,
As a result it is as shown in table 4.
Table 4
It can be seen from the data in table 4 in first set reaction, relative to mono- quaternary alkylphosphonium salt ionic liquids
Body [Bu3PC14H29]+Cl-, quaternary phosphonium salt ionic liquids are prepared in embodiment of the present invention 1-8 to be used to urge
Change the esterification of acetic acid and n-butanol, the reaction time is short, and crude product evaporates in obtained n-butyl acetate
Acetic acid is not contained in point, illustrates that acetic acid is converted completely, esterification carries out complete；In addition, the concentrated sulfuric acid is used
When the esterification of acetic acid and n-butanol is catalyzed, in obtained n-butyl acetate containing positive dibutyl ethers and
The accessory substances such as sulfate pentahydrate, reaction selectivity is relatively low, and the season prepared in embodiment of the present invention 1-8
During the esterification of the ionic liquid-catalyzed acetic acid of phosphonium salt and n-butanol, crude product in obtained n-butyl acetate
Accessory substance, i.e. reaction selectivity are not detected in cut high.
In the second secondary response, the concentrated sulfuric acid can not be reused, and be prepared into embodiment of the present invention 1-8
It can be reused to quaternary phosphonium salt ionic liquids, especially embodiment 1,2,5 and 6 is prepared
Quaternary phosphonium salt ionic liquid is re-used for catalysis acetic acid and positive fourth after being reclaimed through first time catalytic esterification
The esterification of alcohol, the reaction time is constant, does not contain acetic acid still in obtained crude product cut, that is, is catalyzed
Property retention is constant.This explanation is the present invention provide quaternary phosphonium salt ionic liquids as catalyst, is not only catalyzed
Performance is high, and it is good to recycle performance.And in preferred [Bu3PC14H29]+[PTSA]-、[Bu3PC14H29]+
[CF3SO3]-、[Bu3PC12H25]+[PTSA]-[Bu3PC12H25]+[CF3SO3]-In the case of , quaternary alkylphosphonium salts
Ionic liquid is higher as the catalytic performance of catalyst, recycles performance more preferable.
Testing example 3-7
Testing example 3-7 is used to illustrate that the present invention prepares quaternary phosphonium salt ionic liquid catalytic esterifications
Purposes, operating procedure and characterizing method are identical with testing example 2, specific reaction condition, reactant,
Catalyst and reaction result are shown in Table 5.
Table 5
The data explanation of table 5, the present invention prepares quaternary phosphonium salt ionic liquids and acts not only as a variety of esterifications
The catalyst of reaction, and catalytic performance is high.
Claims (11)
1. a kind of quaternary phosphonium salt ionic liquid, the formula of the quaternary phosphonium salt ionic liquid is [Bu3PR]+X-, R is
C6-C16Straight or branched alkyl, wherein, X-For p-C7H7SO3 -、CF3SO3 -、HSO4 -Or H2PO4 -。
2. quaternary phosphonium salt ionic liquid according to claim 1, wherein, R is C8-C14Straight chain
Or branched alkyl, X-For p-C7H7SO3 -Or CF3SO3 -。
3. a kind of preparation method of quaternary phosphonium salt ionic liquid, wherein, this method includes：In ion exchange
Under reaction condition, mono- quaternary alkylphosphonium salts are contacted with Bronsted acid, product of contact is obtained；
Wherein, the formula of the mono- quaternary alkylphosphonium salts is [Bu3PR]+Z-, R is C6-C16Straight or branched
Alkyl, Z is halogen；
The formula of the Bronsted acid is H+X-, X-Selected from p-C7H7SO3 -、CF3SO3 -、HSO4 -And H2PO4 -
In at least one.
4. preparation method according to claim 3, wherein, described first relative to 1 mole
Quaternary alkylphosphonium salt, the consumption of the Bronsted acid is 1-2 moles, and the consumption of the Bronsted acid is with the Bronsted acid
X-Amount calculate.
5. preparation method according to claim 4, wherein, described first relative to 1 mole
Quaternary alkylphosphonium salt, the consumption of the Bronsted acid is 1.01-1.2 moles.
6. preparation method according to claim 3, wherein, the ion-exchange reactions condition bag
Include：Temperature is 85-100 DEG C, and the time is 12-20 hours.
7. the preparation method according to claim 3 or 6, wherein, the preparation method also includes：
It is 2~4 that product obtained by mono- quaternary alkylphosphonium salts are contacted with Bronsted acid, which is washed to pH value, obtains washing production
Thing；Then the washing product is subjected to vacuum distillation and suction filtration, obtains product quaternary phosphonium salt ionic liquid.
8. the preparation method according to any one in claim 3-5, wherein, R is C8-C14
Straight or branched alkyl；Z is chlorine；X-For p-C7H7SO3 -Or CF3SO3 -。
9. the preparation-obtained quaternary phosphine salt ion of preparation method in claim 3-8 described in any one
Liquid.
10. use of the quaternary phosphonium salt ionic liquids in catalytic esterification described in claim 1,2 or 9
On the way.
11. purposes according to claim 10, wherein, the carboxylic acid bag used by the esterification
Include at least one in acetic acid, propionic acid, acrylic acid and benzoic acid；Contain hydroxyl used by the esterification
The organic matter of base includes at least one in methanol, ethanol, n-butanol, isoamyl alcohol and n-octyl alcohol.
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